Technical Field
The present invention relates to novel photochromic organic compounds, more specifically novel tetrahydroindolizines with photochromic properties, the synthesis of the photochromic organic compounds, and their use in devices such as optical memories and photoswitches.
Description of the Related Art
The “background” description provided herein is for the purpose of generally presenting the context of the disclosure. Work of the presently named inventors, to the extent it is described in this background section, as well as aspects of the description which may not otherwise qualify as prior art at the time of filing, are neither expressly or impliedly admitted as prior art against the present invention.
Because of the potential applications of photochromic compounds in erasable optical memories and photoswitches, they have attracted significant attention (German Patent Application Publications DE 3823496 A1 19900118: Preparation of crown compounds for use in analytical chemistry, electronics, and fiber and film techniques; DE 3521432 A1 19861218: Indolizines as light-sensitive materials; DE 3320077 A1 19841206: Photochromic spiro compounds; DE 3220257 A1 19831201:Photochromic spiro[1,8-a-tetrahydroindolizines] and their use in radiation-sensitive materials; DE 2906193 A1 19800828: Photochromic spiro[1,8-a-dihydroindolizines]and their use in radiation-sensitive materials; Bouas-Laurent, H.; Dürr, H. Pure Appl. Chem. 2001, 73, 639-665; Dorion, G. H.; Wiebe, A. F. Photochromism; Focal Press: New York, 1970; Photochromism; Brown, G. H., Ed.; Wiley: New York, 1971; Dürr, H.; Bouas-Laurent, H. Photochromism: Molecules and Systems; Elsevier: Amsterdam, 1990; Crano, G. C.; Guglielmetti, R. Organic Photochromic and Thermochromic Compounds; Plenum Press: New York, 1999; McArdle, C. B. Applied Photochromic Polymer Systems; Blackie: Glasgow, 1992; Irie, M. Photo-Reactive Materials for Ultrahigh Density Optical Memory; Elsevier: Amsterdam, 1994; Guglielmeti, R.; Samat, A. Proceedings of the First International Symposium on Organic Photochromism, Molecular Crystals and Liquid Crystals, 1994, 246; Irie, M. In Molecular Switches; Feringa, B. L., Ed.; Wiley-VCH: Weinheim, 2001; pp 37-60; Iri, M. In Organic Photochromic and Thermochromic Compounds; Crano, J. C., Gugielmetti, R. J., Eds.; Plenum Press: New York, 1999; Vol. 1, pp 207-221. Gorodetsky, B.; Branda, N. Adv. Funct. Mater. 2007, 17, 786; Roberts, M. N.; Carling, C. J.; Nagle, J. K.; Branda, N.; Wolf, M. O. J. Am. Chem. Soc. 2009, 131, 16644. Li, Y. N.; Li, Q. Org. Lett. 2012, 14, 4362-4365; Lv, X. Y.; Wang, M. S.; Yang, C.; Wang, G. E.; Wang, S. H.; Lin, R. G.; Guo, G. C. Inorg. Chem. 2012, 51, 4015-4019; Kamiya, H.; Yanagisawa, S.; Hiroto, S.; Itami, K.; Shinokubo, H. Org. Lett. 2011, 13, 6394-6397; Chen, S. J.; Chen, L. J.; Yang, H. B.; Tian, H.; Zhu, W. H. J. Am. Chem. Soc. 2012, 134, 13596-13599; Sciascia, C.; Castagna, R.; Dekermenjian, M.; Martel, R.; Kandada, A. S.; Fonzo, F. D.; Bianco, A.; Bertarelli, C.; Meneghetti, M.; Lanzani, G. J. Phys. Chem. C 2012, 116, 19483-19489; Ishibashi, Y.; Umesato, T.; Kobatake, S.; Irie, M.; Miyasaka, H. J. Phys. Chem. C 2012, 116, 4862-4869; Bertarelli, C.; Bianco, A.; D'Amore, F.; Gallazzi, M. C.; Zerbi, G.; Adv. Funct. Alater. 2004, 14, 357-363; Fukaminato, T.; Doi, T.; Tamaoki, N.; Okuno, K.; Ishibashi, Y.; Miyasaka, H.; Irie, M. J. Am. Chem. Soc. 2011, 133, 4984-4990; Heremans, P.; Gelinck, G. H.; Miiller, R.; Baeg, K.; Kim, D.; Noh, Y. Chem. Mater. 2011, 23, 341-358; Herder, M.; Patzel, M.; Grubert, L.; Hecht, S. Chem. Commun. 2011, 460-462; Kim, M. S.; Maruyama, H.; Kawat, T.; Irie., M. Chem. Mater. 2003, 15, 4539-4543; Sanz-Menez, N.; Monnier, V.; Colombier, I.; Baldeck, B. L.; Irie, M.; Ibanez, A. Dyes Pigments 2011, 89, 241-245; Liu, G.; Pu, S. Z.; Wang, X. M.; Liu, W. J.; Fan, C. B. Dyes Pigments 2011, 90, 89-99; Tsivgoulis, G.; Lehn, J.-M. Angew. Chem., Int. Ed. Engl. 1995, 34, 1119-1122; Tsujioka, T.; Hamada, Y.; Shibata, K. Appl. Phys. Lett. 2001, 78, 2282-2284; Wojtyk, J. T.; Buncel, E.; Kazmaier, P. M. Chem. Commun. 1998, 1703-1704; Tanaka, M.; Nakamura, M.; Salhin, M. A. A.; Ikeda, T.; Kamada, K.; Ando, H. J. Org. Chem. 2001, 66, 1533-1537—each incorporated herein by reference in its entirety). Upon light irradiation, photochromic molecules exhibit reversible color and structural changes. These molecules have the ability to interconvert between different isomers having unique absorption spectra when stimulated with light. In these systems, the changes in the electronic patterns are responsible for the changes in color and in variations in other physical properties such as luminescence, electronic conductance, refractive index, optical rotation, and viscosity. The photomodulation of these properties has the potential to significantly advance optoelectronic technologies such as waveguides, read/write/erase optical information storage systems and actuators. Photochromic molecules can be employed to modulate various physicochemical properties upon light irradiation, and they have received remarkable attention for their potential applications as photoswitches and optical memory systems (Biteau, J.; Chaput, F.; Lahlil, K.; Boilot, J.-P.; Tsivgoulis, G. M.; Lehn, J.-M.; Darracq, B.; Marois, C.; Lévy, Y. Chem. Mater. 1998, 10, 1945-1950; van Delden, R. A.; ter Wiel, K. K. J.; Feringa, B.-L. Chem. Commun. 2004, 200-201; Feringa, B.-L.; van Delden, R. A.; ter Wiel, M. K. J. Molecular Switches; Wiley-VCH: Weinheim, 2001; pp 123-164; Murguly, E.; Norsten, T.; Branda, N. R. Angew. Chem., Int. Ed. 2001, 40, 1752-1755; Norsten, T. B.; Branda, N. R.; Adv. Mater. 2001, 13, 347-349; Kawai, S.; Yamaguchi, T.; Kato, T.; Hatano, S.; Abe, J. Dyes Pigments 2012, 92, 872-876; Kawai, T.; Kunitake, K.; Irie, M. Chem. Lett. 1999, 905-906; Kim, E.; Choi, Y.-K.; Lee, M.-H. Macromolecules 1999, 32, 4855-4860; Moniruzzaman, M.; Sabey, C. J.; Fernando, G. F. Macromolecules 2004, 37, 2572-2577; Lucas, L. N.; van Esch, J.; Kellogg, R. M.; Feringa, B.-L. Chem. Commun. 2001, 759-760; Kang, J. W.; Kim, J.-J.; Kim, E. Appl. Phys. Lett. 2002, 80, 1710-1713; Wang, C.; Batsanov, A. S.; Bryce, M. R.; Sage, I. Synthesis 2003, 2089-2095; Wang, C.; Pålsson, L.-O.; Batsanov, A. S.; Bryce, M. R. J. Am. Chem. Soc. 2006, 128, 3789-799; Kang, J. W.; Kim, J.-J.; Kim, E. Opt. Mater. 2002, 21, 543-548; Myles, A. J.; Branda, N. R. Adv. Funct. Mater. 2002, 12, 167-173; Hugel, T.; Holland, N. B.; Cattani, A.; Moroder, L.; Seitz, M.; Gaub, H. E. Science 2002, 296, 1103-1106; Alonso, M.; Reboto, V.; Guiscardo, L.; San Martin, A.; Rodriguez-Cabello, J. C. Macromolecules 2000, 33, 9480-9482; Wigglesworth, T. G.; Myles, A. J.; Branda, N. R. Eur. J. Org. Chem. 2005, 1233-1238; Horii, T.; Abe, Y.; Nakao, R. J. Photochem. Photobiol., A 2011, 144, 119-129; Peters, A.; Vitols, C.; McDonald, R.; Branda, N. R. Org. Lett. 2002, 5, 1183-1186; Kalyanasundaram, K.; Grätzel, M. Coord. Chem. Rev. 1998, 347; Argazzi, R.; Bignozzi, C. A.; Heimer, T. A.; Castellano, F. N.; Meyer, G. J. Inorg. Chem. 1994, 33, 5741; Tomasulo, M.; Yildiz, I.; Raymo, F. M. Inorg. Chim. Acta 2007, 360, 938-944; Deniz, E.; Cusido, J.; Swaminathan, S.; Battal, M.; Impellizzeri, S.; Sortino, S.; Raymo, F. M. J. Photochem. Photobiol., A 2012, 229, 20-28 Ahmed, S. A.; Weber, C.; Hozien, Z. A.; Hassan, Kh. M.; Abdel-Wahab, A. A.; Dürr, H. Unpublished results; Ahmed, S. A.; Ph. D Thesis, Saarland-Assiut universities, 2000; Burtscher, P.; Dürr, H.; Rheinberger, V.; Salz, U.; German PatDE, 1995, 195200160; Dürr, H.; Gross, H.; Zils, K D. Deutsche Offenlegungs Schrift Pat., 1983, 3220275A1; Burtscher, B.; Dürr, H.; Rheinberger, V.; Salz. U.; IVOCLAR German Pat., 1995, 195200160—each incorporated by reference herein in its entirety). Since the pioneering discovery of photochromic dihydroindolizines (DHIs) and tetrahydroindolizines (THIs), they have been considered as very interesting photochromic families because of their specific properties such as high photo-fatigue resistance, broad absorption spectra in the visible region, high sensitivity to activation with light, and high photochromic reactivity (Dürr, H. Angew. Chem., Int. Ed. 1989, 28, 413-438; Dürr, H. Wiss. Zeitschr. TH Leuna-Merseburg 1984, 26, 664-671; Dürr, H.; Gross, H.; Zils, K. D. DE 3220257, 1983; Chem. Abstr. 1984, 100, 120909; Dürr, H.; Jönsson, H. P.; Bleisinger, H.; Scheidhauer, P.; Dürr, H.; Wintgens, V.; Valat, P.; Kossanyi, J. J. Org. Chem. 1998, 63, 990-1000; Scheidhauer, P.; Münzmay, T.; Spang, P. DE 3521432, 1986; Chem. Abstr. 1987, 106, 102089; Dürr, H.; Janzen, K. P.; Thome, A.; Braun, B. DE 3823496 A1, 1990; Chem. Abstr. 1990, 113, 132224; Dürr, H.; Gross, H.; Zils, K. D.; Hauck, G.; Hermann, H. Chem. Ber. 1983, 116, 3915-3925; Dürr, H.; Spang. P. DE 3320077, 1984; Dürr, H.; Spang, P.; Deutsche Offenlegungs Schrift Pat. 1984, 32 20 2571; Dürr. H.; Jönsson, H.; Scheidhauer, P.; Münzmay, T, Spang, P. Deutsche Offenlegungs Schrift Pat. 1985, 35214325 Chem. Abstr. 1985, 102, 205414; Fromm, R.; Ahmed, S. A.; Hartmann, Th.; Huch, V.; Abdel-Wahab, A. A.; Dürr, H. Eur. J. Org. Chem. 2001, 21, 4077-4080; Weber, C.; Rustemeyer, F.; Dürr, H. Adv. Mater. 1998, 10, 1348-1351; Andreis, C.; Dürr, H.; Wintgens, V.; Valat, P.; Kossanyi, J. Chem. Eur. J. 1997, 3, 509-516; Ahmed, S. A.; Abdel-Wahab, A. A.; Dürr, H. In CRC Handbook of Organic Photochemistry and Photobiology, Chapter 96; Horspool, W. M., Lenci, F., Eds., 2nd ed.; CRC Press: New York, 2003; pp 1-25—each incorporated by reference herein in its entirety).
The exploration of new di- and tetrahydroindolizine structures with improved properties has received significant attention in organic materials science (Dürr, H.; Janzen, K. P.; Thome, A.; Braun, B. DE 3823496 A1, 1990; Chem. Abstr. 1990, 113, 132224; Dürr, H.; Gross, H.; Zils, K. D.; Hauck, G.; Hermann, H. Chem. Ber. 1983, 116, 3915-3925; Dürr, H.; Spang. P. DE 3320077, 1984; Chem. Abstr. 1985, 102, 205414; Fromm, R.; Ahmed, S. A.; Hartmann, Th.; Huch, V.; Abdel-Wahab, A. A.; Dürr, H. Eur. J. Org. Chem. 2001, 21, 4077-4080; Weber, C.; Rustemeyer, F.; Dürr, H. Adv. Mater. 1998, 10, 1348-1351; Andreis, C.; Dürr, H.; Wintgens, V.; Valat, P.; Kossanyi, J. Chem. Eur. J. 1997, 3, 509-516; Ahmed, S. A.; Abdel-Wahab, A. A.; Dürr, H. In CRC Handbook of Organic Photochemistry and Photobiology, Chapter 96; Horspool, W. M., Lenci, F., Eds., 2nd ed.; CRC Press: New York, 2003; pp 1-25; Ahmed, S. A.; Hartmann, Th.; Huch, V.; Dürr, H.; Abdel-Wahab, A. A. J. Phys. Org. Chem. 2000, 13, 539-548; Tan, Y.; Ahmed, S. A.; Dürr, H.; Huch, V.; Abdel-Wahab, A. A. Chem. Commun. 2001, 1246-1247—each incorporated by reference herein in its entirety). Suitable functionalization in both regions (region A is fluorene, region B is the ester or cyano groups, and region C is the heterocyclic base part) of the DHI skeleton with different substituents can modify effectively the photochromic behavior of dihydroindolizines (Ahmed, S. A. Mol. Cryst. Liq. Cryst. 2005, 430, 295-300; Ahmed, S. A.; Dürr, H. Mol. Cryst. Liq. Cryst. 2005, 431, 275-280; Ahmed, S. A. Monatsh. Chem. 2004, 135, 1173-1188; Ahmed, S. A.; Abdel-Wahab, A. A.; Dürr, H. J. Photochem. Photobiol. 2003, 154, 131-144; Ahmed, S. A. J. Phys. Org. Chem. 2002, 15, 392-402; Ahmed, S. A. J. Phys. Org. Chem. 2006, 19, 402-414; Ahmed, S. A. J. Phys. Org. Chem. 2007, 20, 564-588; Ahmed, S. A.; Hartmann, Th.; Dürr, H. J. Photochem. Photobiol. 2008, 200, 50-56; Ahmed, S. A.; Pozzo, J. L. J. Photochem. Photobiol. 2008, 200, 57-67—each incorporated by reference herein in its entirety).
The position of the substituents is also important for fine-tuning of their optoelectronic properties (Andreis, C.; Dürr, H.; Wintgens, V.; Valat, P.; Kossanyi, J. Chem. Eur. J. 1997, 3, 509-516; Ahmed, S. A.; Abdel-Wahab, A. A.; Dürr, H. In CRC Handbook of Organic Photochemistry and Photobiology, Chapter 96; Horspool, W. M., Lenci, F., Eds., 2nd ed.; CRC Press: New York, 2003; pp 1-25; Ahmed, S. A.; Hartmann, Th.; Huch, V.; Dürr, H.; Abdel-Wahab, A. A. J. Phys. Org. Chem. 2000, 13, 539-548; Tan, Y.; Ahmed, S. A.; Dürr, H.; Huch, V.; Abdel-Wahab, A. A. Chem. Commun. 2001, 1246-1247; Ahmed, S. A. Mol. Cryst. Liq. Cryst. 2005, 430, 295-300; Ahmed, S. A.; Dürr, H. Mol. Cryst. Liq. Cryst. 2005, 431, 275-280; Ahmed, S. A. Monatsh. Chem. 2004, 135, 1173-1188; Ahmed, S. A.; Abdel-Wahab, A. A.; Dürr, H. J. Photochem. Photobiol. 2003, 154, 131-144; Ahmed, S. A. J. Phys. Org. Chem. 2002, 15, 392-402; Ahmed, S. A. J. Phys. Org. Chem. 2006, 19, 402-414; Ahmed, S. A. J. Phys. Org. Chem. 2007, 20, 564-588; Ahmed, S. A.; Hartmann, Th.; Dürr, H. J. Photochem. Photobiol. 2008, 200, 50-56; Ahmed, S. A.; Pozzo, J. L. J. Photochem. Photobiol. 2008, 200, 57-67—each incorporated by reference herein in its entirety). So far, related research has been mainly focused on the effects of substitutents on the fluorene and pyridazine moieties in the dihydroindolizine photochromes (Dürr, H.; Janzen, K. P.; Thome, A.; Braun, B. DE 3823496 A1, 1990; Chem. Abstr. 1990, 113, 132224; Dürr, H.; Gross, H.; Zils, K. D.; Hauck, G.; Hermann, H. Chem. Ber. 1983, 116, 3915-3925; Dürr, H.; Spang. P. DE 3320077, 1984; Chem. Abstr. 1985, 102, 205414; Fromm, R.; Ahmed, S. A.; Hartmann, Th.; Huch, V.; Abdel-Wahab, A. A.; Dürr, H. Eur. J. Org. Chem. 2001, 21, 4077-4080; Weber, C.; Rustemeyer, F.; Dürr, H. Adv. Mater. 1998, 10, 1348-1351; Andreis, C.; Dürr, H.; Wintgens, V.; Valat, P.; Kossanyi, J. Chem. Eur. J. 1997, 3, 509-516; Ahmed, S. A.; Abdel-Wahab, A. A.; Dürr, H. In CRC Handbook of Organic Photochemistry and Photobiology, Chapter 96; Horspool, W. M., Lenci, F., Eds., 2nd ed.; CRC Press: New York, 2003; pp 1-25; Ahmed, S. A.; Hartmann, Th.; Huch, V.; Dürr, H.; Abdel-Wahab, A. A. J. Phys. Org. Chem. 2000, 13, 539-548; Tan, Y.; Ahmed, S. A.; Dürr, H.; Huch, V.; Abdel-Wahab, A. A. Chem. Commun. 2001, 1246-1247; Ahmed, S. A. Mol. Cryst. Liq. Cryst. 2005, 430, 295-300; Ahmed, S. A.; Dürr, H. Mol. Cryst. Liq. Cryst. 2005, 431, 275-280; Ahmed, S. A. Monatsh. Chem. 2004, 135, 1173-1188; Ahmed, S. A.; Abdel-Wahab, A. A.; Dürr, H. J. Photochem. Photobiol. 2003, 154, 131-144; Ahmed, S. A. J. Phys. Org. Chem. 2002, 15, 392-402; Ahmed, S. A. J. Phys. Org. Chem. 2006, 19, 402-414; Ahmed, S. A. J. Phys. Org. Chem. 2007, 20, 564-588; Ahmed, S. A.; Hartmann, Th.; Dürr, H. J. Photochem. Photobiol. 2008, 200, 50-56; Ahmed, S. A.; Pozzo, J. L. J. Photochem. Photobiol. 2008, 200, 57-67; Dürr, H. Chimica 1994, 514-515; Masson, J.-F.; Hartmann, Th.; Dürr, H.; Booksh, K. S. Opt. Mater. 2004, 27, 435-439; Terazono, Y.; Kodis, J.; Andreasson, J.; Jeong, G.; Brune, A.; Hartmann, Th.; Dürr, H.; Moore, A. L.; Moore, Th. M.; Gust, D. J. Phys. Chem. 2004, 108, 1812-1814; Kodis, G.; Liddell, P. A.; de la Garza, L.; Clausen, P. C.; Lindsey, J. S.; Moore, A. L.; Moore, T. A.; Gust, D. J. Phys. Chem. A 2002, 106, 2036-2048; Shrestha, T. B.; Melin, J.; Liu, Y.; Dolgounitcheva, O.; Zakrzewski, V. G.; Pokhrel, M. R.; Gogritchiani, E.; Ortiz, J. V.; Turro, C.; Bossmann, S. H. Photochem. Photobiol. Sci. 2008, 7, 1449-1456; Shrestha, T. B.; Kalita, M.; Pokhrel, M. J.; Liu, Y.; Troyer, D. L.; Turro, C.; Bossmann, S. H.; Dürr, H. J. Org. Chem. 2013, 78, 1903-1909; Gogritchiani, E.; Hartmann, Th.; Palm, B.; Samsoniya, Sh.; Dürr, H. J. Photochem. Photobiol., B 2002, 67, 18-22; Ahmed, S. A. Tetrahedron 2009, 65, 1373-1388; Ahmed, S. A.; Khairou, K. S.; Abdel-Wahab, A. A.; Hozien, Z. A.; Dürr, H. Tetrahedron Lett. 2012, 53, 4397-4401; Ahmed, S. A.; Al-Raqa, S. Y.; Moussa, Z.; Hozien, Z. A.; Abdel-Wahab, A. A.; Al-Simaree, A. A.; Al-Amri, S. N.; Soliman, A. S.; Dürr, H. Tetrahedron 2011, 67, 7173-7184—each incorporated by reference herein in its entirety).
Reports on photochromic tetrahydroindolizines (THIs) are few. Such molecules undergo a photoinduced change of color in solution, solid state, and in polymer matrices when exposed to UV irradiation or direct sunlight, and return to their initial state when the illumination ceases, normally via a thermal pathway. The photochromic behavior of THIs (FIG. 1) is based on a reversible pyrroline ring-opening, induced by light, which converts a colorless form (usually named the ‘closed form’) into the colored form (betaine form) (Ahmed, S. A. Mol. Cryst. Liq. Cryst. 2005, 430, 295-300; Ahmed, S. A.; Dürr, H. Mol. Cryst. Liq. Cryst. 2005, 431, 275-280; Ahmed, S. A. Monatsh. Chem. 2004, 135, 1173-1188; Ahmed, S. A.; Abdel-Wahab, A. A.; Dürr, H. J. Photochem. Photobiol. 2003, 154, 131-144; Ahmed, S. A. J. Phys. Org. Chem. 2002, 15, 392-402; Ahmed, S. A. Phys. Org. Chem. 2006, 19, 402-414—each incorporated by reference herein in its entirety).
Few reports on photochromic THIs showed that the thermal reverse reaction, the 1,5-electrocyclization from the ring-open betaine to the THI shows rates extending from milliseconds to several weeks (Ahmed, S. A. Mol. Cryst. Liq. Cryst. 2005, 430, 295-300; Ahmed, S. A.; Dürr, H. Mol. Cryst. Liq. Cryst. 2005, 431, 275-280; Ahmed, S. A. Monatsh. Chem. 2004, 135, 1173-1188; Ahmed, S. A.; Abdel-Wahab, A. A.; Dürr, H. J. Photochem. Photobiol. 2003, 154, 131-144; Ahmed, S. A. J. Phys. Org. Chem. 2002, 15, 392-402—each incorporated by reference herein in its entirety), depending on the substituents and structure of the molecule involved. This interesting wide range in the lifetime of the colored form allows these molecules to find many versatile applications as shown by DHI photochromes (Ahmed, S. A. Tetrahedron 2009, 65, 1373-1388; Ahmed, S. A.; Khairou, K. S.; Abdel-Wahab, A. A.; Hozien, Z. A.; Dürr, H. Tetrahedron Lett. 2012, 53, 4397-4401; Ahmed, S. A.; Al-Raqa, S. Y.; Moussa, Z.; Hozien, Z. A.; Abdel-Wahab, A. A.; Al-Simaree, A. A.; Al-Amri, S. N.; Soliman, A. S.; Dürr, H. Tetrahedron 2011, 67, 7173-7184; DE 3823496 A1 19900118: Preparation of crown compounds for use in analytical chemistry, electronics, and fiber and film techniques; DE 3521432 A1 19861218: Indolizines as light-sensitive materials DE 3320077 A1 19841206: Photochromic spiro compounds; DE 3220257 A1 19831201: Photochromic spiro[1,8-a-tetrahydroindolizines] and their use in radiation-sensitive materials; DE 2906193 A1 19800828: Photochromic spiro[1,8-a-dihydroindolizines] and their use in radiation-sensitive materials—each incorporated by reference herein in its entirety).